Determinação da reatividade e análise termodinâmica de transportadores sólidos de oxigênio para recirculação química

Abstract

Existing technologies for CO2 capture and sequestration oftentimes make the process industrially infeasible because it demands a high power consumption, leading to a reduction in plant efficiency and increasing the cost of production. Therefore, in order to mitigate the emission of greenhouse gases, has focused on the use of alternative energy and increased efficiency in conversion and use of energy. Chemical Looping Combustion (CLC) and Reform (CLR) are among the best alternatives to reduce CO2 emissions, because they facilitate his capture with low cost and without substantial loss of energy efficiency. The reaction system is based on oxygen transfer on the air into a fuel through a solid oxygen carrier (SOC) which circulates between two fluidized bed reactors. Combustion reactions occur on the surface of the SOC, which is, key issue for the development and sizing from CLC technology. In view of that there is still the necessity of study the behavior of SOCs in order to obtain a suitable carrier for the chemical looping technology, this work had as objective carry out a study of the SOCs for CLC and CLR using hydrogen, methane and ethanol as fuels. Two SOCs, to the based on Ni and Cu, were assessed according their reactivities, as well as the thermodynamic study was performed for this process. For this study, an characterization of SOC to Cu base was perfomed different mass concentrations of Cu. The results showed that the concentration of copper to be added to the support decreased size pore inflict on by sintering of the active metal, leaving only a percentage at the surface. Significant changes in the reduction temperature were not observed with the increase in Cu concentration. In general, all the SOC to Cu base reached maximum conversion using ethanol as fuel, showing to be quite reactive. It was also found that the higher the metal oxide content, the lower the reaction rate. For the addition of low concentrations of copper, the nucleation model showed better description of the experimental data. Already for the higher concentrations of copper addition and with addition of 1% cerium, the shrinking core model correlated better to experimental data. Regarding the redox system CuO / Cu, it was observed that high values of equilibrium constant (Keq) were obtained for the temperatures investigated, showing virtually complete conversion of the fuel is obtained. Increasing the temperature resulted in a decrease of Keq, but higher temperatures are required for complete reduction of the SOC. The variation of Gibbs energy was minimal for the relevant temperatures for CLC, indicating that the combustion reaction occurs spontaneously. For Ni-based SOC, commercial samples were used. This proved to be very reactive, with conversions greater than 90% using CH4 and H2 and CH4 + H2O as fuels. High temperatures, around 900 °C were required for a high conversion. The shrinking core model obtained a good description of the experimental data presenting low error for lower conversions than 0.8, while the diffusion model described better the experimental data with conversions greater than 0.8.